Harnessing Metastable Byproducts: A Dual-Regulation Strategy for Intrinsically Stable High-Voltage Spinel Cathodes

Qianchen Wang; Zhonghao Lv; Zimo Zhang; Junkai Zhang; Liyao Lu; Yuhang Xin; Yingshuai Wang; Hongcai Gao

doi:10.1021/acs.chemmater.6c00887

Harnessing Metastable Byproducts: A Dual-Regulation Strategy for Intrinsically Stable High-Voltage Spinel Cathodes

Qianchen Wang^*
, Zhonghao Lv
, Zimo Zhang
, Junkai Zhang
, Liyao Lu
, Yuhang Xin
, Yingshuai Wang
, Hongcai Gao^*

^*Corresponding author for this work

Tiangong University
Hubei University of Automotive Technology
Wuhan University of Science and Technology
Beijing Institute of Technology

Research output: Contribution to journal › Article › peer-review

Abstract

Spinel LiNi_0.5Mn_1.5O₄ (LNMO) suffers from Mn³⁺-induced degradation due to thermodynamic phase separation. Herein, we report the preincorporation of a Li_xNi_1–xO (LNO) phase to regulate oxygen behavior through a dual-regulation strategy (interfacial charge modulation and kinetic facilitation of oxygen diffusion). Differential charge and Bader analyses confirm that the presence of LNO increases the covalency of the Mn–O bond and suppresses the release of oxygen. In situ EIS-DRT shows improved interfacial ion transport and suppressed side reactions. The optimized composite finally showed 54.2% less Mn³⁺, 76.2% higher oxygen vacancy energy, and 98.0% capacity retention over 300 cycles. This work will prove to be an overarching approach to stabilizing metastable cathodes by utilizing deleterious phases.

Original language	English
Pages (from-to)	5744-5752
Number of pages	9
Journal	Chemistry of Materials
Volume	38
Issue number	11
DOIs	https://doi.org/10.1021/acs.chemmater.6c00887
Publication status	Published - 9 Jun 2026
Externally published	Yes

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10.1021/acs.chemmater.6c00887

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title = "Harnessing Metastable Byproducts: A Dual-Regulation Strategy for Intrinsically Stable High-Voltage Spinel Cathodes",

abstract = "Spinel LiNi0.5Mn1.5O4 (LNMO) suffers from Mn3+-induced degradation due to thermodynamic phase separation. Herein, we report the preincorporation of a LixNi1{\textendash}xO (LNO) phase to regulate oxygen behavior through a dual-regulation strategy (interfacial charge modulation and kinetic facilitation of oxygen diffusion). Differential charge and Bader analyses confirm that the presence of LNO increases the covalency of the Mn{\textendash}O bond and suppresses the release of oxygen. In situ EIS-DRT shows improved interfacial ion transport and suppressed side reactions. The optimized composite finally showed 54.2\% less Mn3+, 76.2\% higher oxygen vacancy energy, and 98.0\% capacity retention over 300 cycles. This work will prove to be an overarching approach to stabilizing metastable cathodes by utilizing deleterious phases.",

author = "Qianchen Wang and Zhonghao Lv and Zimo Zhang and Junkai Zhang and Liyao Lu and Yuhang Xin and Yingshuai Wang and Hongcai Gao",

note = "Publisher Copyright: {\textcopyright} 2026 American Chemical Society",

year = "2026",

month = jun,

day = "9",

doi = "10.1021/acs.chemmater.6c00887",

language = "English",

volume = "38",

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journal = "Chemistry of Materials",

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TY - JOUR

T1 - Harnessing Metastable Byproducts

T2 - A Dual-Regulation Strategy for Intrinsically Stable High-Voltage Spinel Cathodes

AU - Wang, Qianchen

AU - Lv, Zhonghao

AU - Zhang, Zimo

AU - Zhang, Junkai

AU - Lu, Liyao

AU - Xin, Yuhang

AU - Wang, Yingshuai

AU - Gao, Hongcai

PY - 2026/6/9

Y1 - 2026/6/9

N2 - Spinel LiNi0.5Mn1.5O4 (LNMO) suffers from Mn3+-induced degradation due to thermodynamic phase separation. Herein, we report the preincorporation of a LixNi1–xO (LNO) phase to regulate oxygen behavior through a dual-regulation strategy (interfacial charge modulation and kinetic facilitation of oxygen diffusion). Differential charge and Bader analyses confirm that the presence of LNO increases the covalency of the Mn–O bond and suppresses the release of oxygen. In situ EIS-DRT shows improved interfacial ion transport and suppressed side reactions. The optimized composite finally showed 54.2% less Mn3+, 76.2% higher oxygen vacancy energy, and 98.0% capacity retention over 300 cycles. This work will prove to be an overarching approach to stabilizing metastable cathodes by utilizing deleterious phases.

AB - Spinel LiNi0.5Mn1.5O4 (LNMO) suffers from Mn3+-induced degradation due to thermodynamic phase separation. Herein, we report the preincorporation of a LixNi1–xO (LNO) phase to regulate oxygen behavior through a dual-regulation strategy (interfacial charge modulation and kinetic facilitation of oxygen diffusion). Differential charge and Bader analyses confirm that the presence of LNO increases the covalency of the Mn–O bond and suppresses the release of oxygen. In situ EIS-DRT shows improved interfacial ion transport and suppressed side reactions. The optimized composite finally showed 54.2% less Mn3+, 76.2% higher oxygen vacancy energy, and 98.0% capacity retention over 300 cycles. This work will prove to be an overarching approach to stabilizing metastable cathodes by utilizing deleterious phases.

UR - https://www.scopus.com/pages/publications/105041333760

U2 - 10.1021/acs.chemmater.6c00887

DO - 10.1021/acs.chemmater.6c00887

M3 - Article

AN - SCOPUS:105041333760

SN - 0897-4756

VL - 38

SP - 5744

EP - 5752

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 11

ER -

Harnessing Metastable Byproducts: A Dual-Regulation Strategy for Intrinsically Stable High-Voltage Spinel Cathodes

Abstract

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